Organopolysiloxanes containing hydrophilic groups

ABSTRACT

The invention relates to organopolysiloxanes containing hydrophilic groups, processes for their preparation and their use in organopolysiloxane compositions which are crosslinkable upon intake of moisture.

FIELD OF THE INVENTION

The present invention relates to organopolysiloxanes containinghydrophilic groups, processes for their preparation and their use inorganopolysiloxane compositions which are crosslinkable upon intake ofmoisture.

In the present invention, the term organopolysiloxanes also includesoligomeric siloxanes.

BACKGROUND OF INVENTION

Owing to their low polarity, diorganopolysiloxanes most often exhibit ahydrophobic surface. It is of great importance to increase theirhydrophilicity, for example, in silicone-based dental impressioncompounds in order to improve water wettability, in sealing compounds inorder to improve overcoatability with aqueous emulsion paints, and inthe surface treatment of fibers or textiles in order to improve thehandle. The use of organopolysiloxanes containing polar groups allowsthe modification of the polarity and thus the surface energy in such amanner that the hydrophilicity of the siloxane is improved. Owing totheir commercial availability, their neutrality and the relatively highchemical stability, polyether radicals are often used as the polargroups. See U.S. Pat. No. 3,565,845 (Union Carbide Corp; issued on Feb.23, 1971) and corresponding DE-B 1,947,268 and U.S. Pat. No. 4,657,959(Minnesota Mining Mfg Co., issued on Apr. 14, 1987) and correspondingWO-A 87/03001.

In cases wherein crosslinkability of the hydrophilic organopolysiloxaneis desirable, in order to increase the durability of the hydrophilicproperties the siloxane skeleton must contain further crosslinkablegroups. See U.S. Pat. No. 4,283,519 (Union Carbide Corp., issued on Jul.22, 1981) and the corresponding EP-A 32310 and U.S. Pat. No. 4,552,919(Toray Silicone Co. Ltd., issued on Nov. 12, 1985). The disadvantage ofsuch compositions is that crosslinking of the hydrolyzable functionsupon intake of moisture is only possible at elevated temperature and/orin the presence of metal catalysts.

SUMMARY OF INVENTION

The present invention relates to organopolysiloxanes comprising at leastone unit (A) of the formula

    (R.sup.3 O).sub.m SiHR.sub.2-m O.sub.1/2                   (I)

and at least one unit (B) selected from the group consisting of ER₂SiO_(1/2), ERSiO_(2/2) and ESiO_(3/2), in which

R is monovalent SiC-bonded optionally substituted hydrocarbon radicalshaving 1 to 12 carbon atoms,

R³ is monovalent optionally substituted hydrocarbon radicals,

m is 1 or 2, and

E is a radical of the formula

    --R.sup.1.sub.n [OY].sub.x R.sup.2                         (II)

in which

R¹ is an alkylene radical having 1 to 6 carbon atoms,

n is 0 or 1,

Y consists of alkylene groups having 1 to 4 carbon atoms,

R² is an alkoxy radical having 1 to 6 carbon atoms or anoxycarbonylalkyl radical having 1 to 6 carbon atoms, and

x is an integer from 1 to 200.

The proportion of siloxane units (A) is preferably between 0.2% and 67%,more preferably between 1% and 10%, relative to the total number of thesiloxane units present in the organopolysiloxane.

The proportion of siloxane units (B) is preferably between 1% and 70%,more preferably between 1% and 40%, relative to the total number of thesiloxane units present in the organopolysiloxane.

The organopolysiloxanes containing hydrophilic groups are preferablythose of the formula

    [(R.sup.3 O).sub.m HSiR.sub.2-m O.sub.1/2 ].sub.a [(R.sup.3 O)R.sub.2 SiO.sub.1/2 ].sub.b [ER.sub.2 SiO.sub.1/2 ].sub.c [ERSiO.sub.2/2 ].sub.d [R.sub.2 SiO.sub.2/2 ].sub.e [SiO.sub.4/2 ].sub.f [RSiO.sub.3/2 ].sub.g [ESiO.sub.3/2 ].sub.h                                     (III),

in which

R, E, R³ and m have the above mentioned meaning and

a is from 1 to 8,

b and c are each from 0 to 8,

d is 0 to 280,

e is 0 to 396,

f is 0 to 3,

g is 0 to 6, and

h is 0 to 3, wherein

a+b+c is 2 to 8,

c+d+h is 1 to 280,

a+b+c+d+e+f+g+h is 3 to 400,

and the ratio of the sum of a+b+e+f+g to that of c+d+h is 100:1 to 1:1.

Examples of radicals R are alkyl radicals, such as methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, sec-butyl,n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl radicals, hexyl radicals,such as n-hexyl, heptyl radicals, such as n-heptyl, octyl radicals, suchas n-octyl, and iso-octyl radicals, such as 2,2,4-trimethylpentyl and2-ethylhexyl, nonyl radicals, such as n-nonyl, decyl radicals, such asn-decyl, dodecyl radicals, such as n-dodecyl; alkenyl radicals, such asvinyl, allyl, 5-hexen-1-yl, E-4-hexen-1-yl, Z-4-hexen-1-yl,2-(3-cyclohexenyl) ethyl and cyclododeca-4,8-dienyl radicals, cycloalkylradicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals andmethylcyclohexyl radicals; aryl radicals, such as phenyl and naphthyl;alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals andethylphenyl radicals; aralkyl radicals, such as benzyl, α- andβ-phenylethyl and 2-phenyl-1-propyl.

Examples of substituted hydrocarbon radicals R are halogen-substitutedhydrocarbon radicals having 1 to 12 carbon atoms, such as alkyl radicalssubstituted by fluorine, chlorine, bromine and iodine atoms, such as3,3,3-trifluoro-n-propyl, 2,2,2,2',2',2'-hexafluoroisopropyl,heptafluoroisopropyl, and haloaryl radicals, such as o-, m- andp-chlorophenyl and mercapto-substituted hydrocarbon radicals having 1 to12 carbon atoms, such as --(CH₂)₃ SH, --(CH₂)₆ SH, --(CH₂)₄ CH(SH)CH₃,2-(3-mercapto-1-cyclohexyl)-1-ethyl,2-(3,4-dimercapto-1-cyclohexyl)-1-ethyl, --(CH₂)3O(CH₂)₃ SH, --(CH₂)₃OCH₂ CH(SH)CH₂ SH, --(CH₂)₃ OCH₂ CH(SH)CH₃, --(CH₂)₃ OOC--CH₂ SH,--(CH₂)₃ OOC(CH₂)₂ SH, --(CH₂)₈ SH, --(CH₂)₆ CH(SH)CH₃, --(CH₂)₇ SH,--CH₂ SH, --(CH₂)₂ SH, --(CH₂)₅ CH═CH(CH₂)₅ SH, --(CH₂ )₅ CH═CH(CH₂)₃CH(SH)CH₃, --(CH₂)₅ CH(SH)(CH₂)₄ CH═CH₂, --(CH₂)₆ CH(SH)(CH₂)₃ CH═CH₂,--(CH₂)₆ CH(SH)(CH₂)₃ CH(SH)CH₃, --(CH₂)₅ CH(SH)(CH₂)₄ CH(SH)CH₃,--(CH₂)₅ CH(SH)(CH₂)₆ SH, --(CH₂)₆ CH(SH)(CH₂)₆ SH,1-mercapto-4-cyclododec-8-enyl, 1-mercapto-5-cyclododec-8-enyl,1,6-dimercapto-10-cyclododecyl, 1-mercapto-2-cyclobutyl,1-mercapto-3-cyclobutyl, 1-mercapto-2-cyclopentyl,1-mercapto-3-cyclopentyl, 1-mercapto-2-cyclohexyl,1-mercapto-3-cyclohexyl, 1-mercapto-4-cyclohexyl,1-mercapto-2-cycloheptyl, 1-mercapto-3-cycloheptyl,1-mercapto-4-cycloheptyl, 1-mercapto-2-cyclooctyl,1-mercapto-3-cyclooctyl, 1-mercapto-4-cyclooctyl,1-mercapto-5-cyclooctyl, 1,2-dimercapto-4-cyclohexyl,1-mercaptocyclohex-3-en-3-yl, 1-mercaptocyclohex-3-en-4-yl,1-mercaptocyclohex-2-en-4-yl, --(CH₂)₃ SCH₂ CH(SH)CH₂ SH, --(CH₂)₃S(CH₂)₃ SH, -ortho--(CH₂)₃ OC₆ H₄ SH, -meta--(CH₂)₃ OC₆ H₄ SH,-para--(CH₂)₃ OC₆ H₄ SH, -ortho-(CH₂)₃ OC₆ H₄ O(CH₂)₃ SH, -meta--(CH₂)₃OC₆ H₄ O(CH₂)₃ SH, -para--(CH₂)₃ OC₆ H₄ O(CH₂)₃ SH, -ortho--(CH₂)₃ C₆ H₄SH, -meta--(CH₂)₃ C₆ H₄ SH, -para--(CH₂)₃ C₆ H₄ SH, -ortho-C₆ H₄ SH,-meta-C₆ H₄ SH, -para-C₆ H₄ SH, --(CH₂)OOC(CH₂)₁₁ SH and --(CH₂)₃OOC(CH₂)₉ CH(SH)CH₃.

Preferred radicals R are methyl, phenyl, vinyl, allyl, 5-hexen-1-ylradicals and linear thioalkyl radicals, such as --(CH₂)₃ SH, --(CH₂)₆ SHand --(CH₂)₄ CH(SH)CH₃, methyl, vinyl and --(CH₂)₃ SH radicals beingmore preferred.

Preferred radicals R³ are monovalent hydrocarbon radicals having 1 to 13carbon atoms which may be substituted by ether oxygen atoms.

Examples of radicals R³ are the examples of alkyl and cycloalkylradicals given for radical R and --(CH₂)₂ --OCH₃, --(CH₂)₂ OCH₂ CH₃ and--(CH₂)₂ --OCH₃.

Preferred radicals R³ are methyl, ethyl, n-propyl, iso-propyl, n-butyland sec-butyl radicals, the ethyl radical being more preferred.

Examples of R¹ are linear or branched alkylene radicals, such asmethylene, ethylene, n-propylene, iso-propylene, 1-n-butylene,2-n-butylene, iso-butylene, tert-butylene, n-pentylene, iso-pentylene,neo-pentylene, tert-pentylene and n-hexylene radicals.

Preferred radicals R¹ are --CH₂ --, --(CH₂)₂ --, --(CH₂)₃ -- and --CH₂CH(CH₃)--, --(CH₂)₃ -- being more preferred.

Examples of Y are the examples of divalent alkylene radicals having 1 to4 carbon atoms given for radical R¹.

Preferred radicals Y are --CH₂ --, --(CH₂)₂ --, --(CH₂)₃ -- and --CH₂CH(CH₃)--, --(CH₂)₂ -- being more preferred.

Radicals R² as alkoxy radicals are linear or branched alkyl radicalshaving 1 to 6 carbon atoms bonded via an oxygen atom. Radicals R² asoxycarbonylalkyl radicals are carboxyl radicals having a linear orbranched alkyl radical. Examples of such alkyl radicals are the alkylradicals having 1 to 6 carbon atoms given for radical R.

Preferred radicals R² are alkoxy radicals, such as methoxy, ethoxy,n-propoxy and n-butoxy radicals, and oxycarbonylalkyl radicals, such asHCOO--, H₃ CCOO-- and (H₃ C)₂ CHCOO-- radicals, methoxy, ethoxy andn-butoxy radicals and H₃ CCOO-- being more preferred.

Preferably, m is 2.

x is preferably an integer between 3 and 60, more preferably between 3and 15.

Apart from the siloxane units mentioned in formula (III), furthersiloxane units such as [(R³ O)_(m-1) HSiR_(2-m) O_(2/2) ] and [(R³ O)₃SiO_(1/2) ] where R, R³ and m have the above mentioned meaning, canadditionally be present to a minor extent as a result of preparation.

In formula (III), the ratio of a+b+e+f+g to x.(c+d+h) is preferably10:90 to 99:1, more preferably 20:80 to 90:10.

The properties of the organopolysiloxanes containing hydrophilic groupscan be adjusted in a simple manner by varying the ratios of the varioussiloxane units to one another and the type of the radical E of theformula (II). Thus, in formula (III), large values of e and small valuesof c, d, h and x improve the miscibility of these compounds withdialkylpolysiloxanes. In contrast, small values of e and large values ofc, d, h and x increase the hydrophilicity of the organopolysiloxaneswith c, d, e, h and x having the meaning given above.

If the organopolysiloxanes are intended to be crosslinked in thepresence of moisture, it is advantageous to select those siloxanes offormula (III) whose a:b+c ratio is greater than or equal to 2:3, morepreferably greater than or equal to 3:2.

If the organopolysiloxanes contain SiC-bonded mercapto-substitutedhydrocarbon radicals and SiC-bonded radicals having an aliphaticcarbon-carbon multiple bond, crosslinking is also possible byirradiation with electromagnetic radiation, resulting in the formationof so-called dual cure systems. See for example, WO 93/00405(Wacker-Chemie GmbH; issued on Jan. 7, 1993).

In order to ensure sufficient photocrosslinkability of theorganopolysiloxanes, the ratio of SiC-bonded mercapto-substitutedhydrocarbon radicals to the SiC-bonded radicals having an aliphaticcarbon-carbon multiple bond is chosen such that it is preferably between10:1 and 1:10, more preferably between 5:1 and 1:5, especially between2:1 and 1:2.

The organopolysiloxanes containing hydrophilic groups preferably have amolecular weight of 500 to 100,000, more preferably 1500 to 60,000.

The organopolysiloxanes containing hydrophilic groups have the advantageof being able to crosslink rapidly upon intake of moisture. Furthermore,they have the advantage of crosslinking very effectively withoutaddition of metal catalysts, such as tin catalysts and titaniumcatalysts. Their pot life can be adjusted as desired without problems byaddition of suitable Bronsted acids.

The organopolysiloxanes containing hydrophilic groups can be prepared bymethods customary in silicon chemistry. They can be prepared by reactingorganopolysiloxanes or organosilanes containing not only at least oneterminal hydroxyl group but also at least one siloxane unit (B) withhydrogenorganyloxysilanes by the procedure described in theinternational application under the file number PCT/EP91/00795(Wacker-Chemie GmbH, submitted on Apr. 25, 1991) and corresponding U.S.Pat. No. 5,304,621, issued on Apr. 19, 1994. The stoichiometry of thereactants is chosen such that at least one siloxane unit (A) is presentin the reaction product. The organopolysiloxanes containing not only atleast one terminal hydroxyl group but also at least one siloxane unit(B) can be prepared by co-hydrolysis of chloro-, acyloxy- oralkoxysilanes, preferably at a pressure of 900 to 1100 hPa and atemperature of 20° to 180° C. See W. Noll "Chemie und Technologie derSilicone", Verlag Chemie Weinheim, 2nd ed. 1968, page 163ff.

The organopolysiloxanes are preferably prepared in a first step by mixedhydrolysis or equilibration and mixed condensation of a silane of theformula

    ERSiZ.sub.2                                                (IV),

with compounds selected from the group consisting of silanes of theformula

    R.sub.2 SiZ.sub.2                                          (V),

organopolysiloxanes of the formula

    HO(SiR.sub.2 O).sub.i H                                    (VI),

and cyclic siloxanes of the formula

    (SiR.sub.2 O).sub.j                                        (VII),

followed by reaction of the hydroxyl-containing organosilicon compoundthus obtained in a second step with a silane of the formula

    (R.sup.3 O).sub.m HSiR.sub.2-m X                           (XII),

in which

E, R, R³ and m have the above mentioned meaning,

Z is a hydroxyl group or a group which can be easily hydrolyzed, such asa halogen atom, an alkoxy radical or an oxycarbonylalkyl radical,

i is an integer from 2 to 2000,

j is an integer from 3 to 6, and

X is a group which can be easily eliminated, such as a halogen atom and--OR³, --NR--C(═O)R, --OC(═O)R and --NR₂ radicals.

To prepare organopolysiloxanes of formula (III) where c>0, silanes ofthe formula

    ER.sub.2 SiZ                                               (VIII)

where

E, R and Z have the above mentioned meaning, are added.

To prepare organopolysiloxanes of formula (III) where h>0, silanes ofthe formula

    ESiZ.sub.3                                                 (IX)

where

E and Z have the above mentioned meaning, are added.

To prepare organopolysiloxanes of formula (III) where f>0, silanes ofthe formula

    SiZ.sub.4                                                  (X)

where

Z has the above mentioned meaning, are added.

To prepare organopolysiloxanes of formula (III) where g>0, silanes ofthe formula

    RSiZ.sub.3                                                 (XI)

where

R and Z have the above mentioned meaning, are added.

In the process, the silanes of formulae (IV), (V), (VIII), (IX), (X) and(XI) can also be used in the form of homo- or co-oligomers, which areformed by complete or incomplete hydrolysis and condensation, as can bemixtures of silanes of formulae (IV), (V), (VIII), (IX), (X) and (XI)and homo- or co-oligomers thereof.

Examples of the radical Z are fluorine, chlorine, bromine and iodineatoms and methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy sec-butoxy,iso-butoxy, 2-methoxyethyl, 2-butoxyethyl, acetoxy and formyloxyradicals, preferably chlorine, methoxy, ethoxy, iso-propoxy and acetoxyradicals.

Preferably, X is the radical --OR³ where R³ has the above mentionedmeaning.

In the process, equilibration can be carried out in the presence of anacid catalyst. Preferred acid catalysts are phosphornitrilic chlorides,such as those described in U.S. Pat. No. 3,839,388 (Wacker-Chemie;issued on Oct. 1, 1974) and the corresponding DE-A 2,229,514 and U.S.Pat. No. 5,008,229 (Wacker-Chemie; issued on Apr. 16, 1991) and thecorresponding DE-A 3,903,137.

In the process, the silanes of formulae (IV), (V), (VIII), (IX), (X) and(XI) are preferably chosen for equilibration wherein at least 5 molpercent of all radicals Z are halogen atoms, more preferably chlorineatoms.

The hydroxyl groups formed are stabilized by subsequent hydrolysis ormixed hydrolysis of compounds (IV) to (XI), preferably in the presenceof base, such as NaHCO₃, MgO, K₂ CO₃, Na₂ CO₃ and/or amines, such asammonia, triethylamine or dibutylamine, which can be used as such or inthe form of their aqueous solutions.

The first step of the process is preferably carried out at a temperatureof 20° to 120° C. and a pressure of 900 to 1100 hPa.

The second step of the process is preferably carried out at atemperature of 80° to 120° C. and a pressure of 900 to 1100 hPa.

Apart from the siloxane units mentioned in formula (III), furthersiloxane units can additionally be present to a minor extent as aconsequence of the chosen method of synthesis.

Furthermore, the organopolysiloxanes prepared can also be present in themixture with secondary components consisting of the silanes of formulae(IV), (VIII) and (IX), such as HR¹ _(n) [OY]_(x) R² where R¹, R², Y andx have the above mentioned meaning, such as H(OCH₂ CH₂)₆ --OCH₃ and H₃CCH₂ CH₂ --(OCH₂ CH₂)₆ --OCH₃, and secondary components resulting fromthe reaction, such as cyclosiloxanes.

Examples of silanes of formula (IV) are H₃ CSiCl₂ --(CH₂)₃ O(CH₂ CH₂ O)₅CH₃, H₃ CSi(OCH₃)₂ --(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃, H₃ CSi(OCH(CH₃)₂)₂--(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃, H₃ CSi(OCH(CH₃)₂)₂ --(CH₂)₃ O(CH₂ CH₂ O)₁₅CH₃, H₃ CSi(OCH₂ CH₃)₂ --(CH₂)₃ O(CH₂ CH₂ O)₄₄ CH₃, H₃ CSi(OCH₃)₂--(CH₂)₃ O(CH₂ CHCH₃ O)₂₄ (CH₂ CH₂ O)₄₈ (CH₂)₃ CH₃, H₃ CSi(OCH₃)₂--(CH₂)₃ O(CH₂ CHCH₃ O)₆₆ (CH₂)₃ CH₃, H₃ CSiCl₂ --O(CH₂ CH₂ O)₅ CH₃,PhSiCl₂ --(CH₂)₆ O(CH₂ CH₂ O)₅ CH₃, H₃ CSi(OCH₂ CH₂ CH₃)₂ --(CH₂)₃ O(CH₂CH₂ O)₇ CH₃, H₃ CSiCl(OCH₂ CH₃)--(CH₂)₃ O(CH₂ CH₂ O)₃ CH₃, H₃CSi(OCH(CH₃)₂)₂ --(CH₂)₃ O(CH₂ CH₂ CH₂ O)₃₃ (CH₂)₃ CH₃, H₃ CSi(OCH₃)₂--(CH₂)₃ O(CH₂ CH₂ O)₁₅ OCCH₃ and H₃ CSi(OCH₃)₂ --(CH₂)₃ O(CH₂ CH₂ O)₄₄OCCH(CH₃)₂, preference being given to H₃ CSiCl₂ --(CH₂)₃ O(CH₂ CH₂ O)₅CH₃, H₃ CSi(OCH₃)₂ --(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃ and H₃ CSi(OCH(CH₃)₂)₂--(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃.

Examples of silanes of formula (V) are (H₃ C)₂ SiCl₂, H₂C═CH--Si(CH₃)Cl₂, Ph₂ SiCl₂, Ph(H₃ C)SiCl₂, H₂ C═CH--(CH₂)₄--Si(CH₃)Cl₂, (H₂ C═CH)PhSiCl₂, (F₃ CCH₂ CH₂)(H₃ C)SiCl₂, (F₃ CCH₂CH₂)(H₃ C)Si(OCH₃)₂, (F₃ CCH₂ CH₂)(H₃ C)Si(OCH₃)Cl,2-(3-cyclohexenyl)-ethyl-Si(CH₃)Cl₂, (H₃ C)₂ Si(OCH₃)₂, H₂C═CH--Si(CH₃)(OCH₃)₂, Ph₂ Si(OCH₃)₂, Ph(H₃ C)Si(OCH₃)₂, H₂ C═CH--(CH₂)₄--Si(CH₃)(OCH₃)₂, (H₂ C═CH)PhSi(OCH₃)₂,2-(3-cyclohexenyl)-ethyl-Si(CH₃)(OCH₃)₂, HS--CH₂ --Si(CH₃)(OCH₃)₂,HS--(CH₂)₃ --Si(CH₃)(OCH₃)₂, (H₃ C)₂ Si(OCH₂ CH₃)₂, H₂C═CH--Si(CH₃)(OCH₂ CH₃)₂, H₂ C═CH--Si(CH₃) (OOCCH₃)₂, (H₃ C)₂Si(OOCCH₃)₂, Ph₂ Si(OCH₂ CH₃)₂, Ph(H₃ C)Si(OCH₂ CH₃)₂ and H₃CCH═CH--(CH₂)₃ --Si(CH₃)(OCH₂ CH₃)₂, where Ph is a phenyl radical,preferably (H₃ C)₂ SiCl₂, H₂ C═CH--Si(CH₃)Cl₂, and HS(CH₂)₃--Si(CH₃)(OCH₃)₂.

Examples of siloxanes of formula (VI) are HO[Si(CH₃)₂ O]₂ H, HO[Si(CH₃)₂O]₁₅ H, HO[Si(CH₃)₂ O]₃₅ H, HO[Si(CH₃)₂ O]₆₅ H, HO[Si(CH₃)₂ O]₁₀₈ H,HO[Si(CH₃)₂ O]₂₂₀ H, HO[Si(CH₃)₂ O]₆₄₄ H, HO[Si(CH₃)₂ O]₉₂₀ H,HO[Si(CH₃)₂ O]₁₄₅₀ H, HO[Si(CH₃)₂ O]₄₄ [Si(CH═CH₂)CH₃ O]₁₁ H,HO[Si(CH═CH₂)CH₃ O]₅₇ H, HO[Si(CH₃)₂ O]₅₈ [Si(Ph)CH₃ O]₄ H, HO[Si(CH₃)₂O]₁₁₈ [Si(Ph)₂ O]₁₄ H, HO[Si(CH₃)(CH₂ CH₂ CF₃)O]₄ H, HO[Si(CH₃)(CH₂ CH₂CF₃)O]₂₃ H, HO[Si(CH₃)(CH₂ CH₂ CF₃)O]₈₃ H, HO[Si(CH₃)(CH₂ CH₂ CF₃)O]₁₀₂H, and HO[Si(CH₃)₂ O]₇₄ [Si(CH═CH₂)CH₃ O]₄ [HS--(CH₂)₃ --Si(CH₃)O]₂ Hwhere Ph is a phenyl radical, preference being given to HO[Si(CH₃)₂ O]₃₅H, HO[Si(CH₃)₂ O]₂₂₀ H, HO[Si(CH₃)₂ O]₆₄₄ H, and HO[Si(CH₃)₂ O]₄₄[Si(CH═CH₂)CH₃ O]₁₁ H.

Examples of siloxanes of formula (VII) are [Si(CH₃)₂ O]₃, [Si(CH₃)₂ O]₄,[Si(CH₃)₂ ]₅, [Si(CH₃)₂ O]₆, [Si(CH₃)PhO]₃, [Si(CH₃)PhO]₄,[Si(CH₃)PhO]₅, [Si(CH₃)PhO]₆, [SiPh₂ O]₃,[SiPh₂ O]₄, [SiPh₂ O]₅, [SiPh₂O]₆, [Si(CH₃)(CH₂ CH₂ CF₃)O]₃, [Si(CH₃)(CH₂ CH₂ CF₃)O]₄, [Si(CH₃)(CH₂CH₂ CF₃)O]₅, [Si(CH₃)(CH₂ CH₂ CF₃)O]₆, [Si(CH₃)(CH═CH₂)O]₃,[Si(CH₃)(CH═CH₂)O]₄, [Si(CH₃)(CH═CH₂)O]₅ and [Si(CH₃)(CH═CH₂)O]₆ wherePh is a phenyl radical, preference being given to [Si(CH₃)₂ O]₃,[Si(CH₃)₂ O]₄, [Si(CH₃)₂ O]₅, [Si(CH₃)(CH₂ CH₂ CF₃)O]₃, and[Si(CH₃)(CH═CH₂)O]₄.

Examples of silanes of formula (VIII) are (H₃ C)₂ SiOH--(CH₂)₃ O(CH₂ CH₂O)₅ CH₃, (H₃ C)₂ SiCl--(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃, (H₃ C)₂Si(OCH₃)--(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃, (H₃ C)₂ Si(OCH(CH₃)₂)--(CH₂)₃ O(CH₂CH₂ O)₁₅ CH₃, (H₃ C)₂ SiCl--(CH₂)₃ O(CH₂ CH₂ O)₄₄ CH₃, (H₃ C)₂Si(OCH₃)--(CH₂)₃ O(CH₂ CHCH₃ O)₂₄ (CH₂ CH₂ O)₄₈ (CH₂)₃ CH₃, (H₃ C)₂Si(OCH₃)--(CH₂)₃ O(CH₂ CHCH₃ O)₆₆ (CH₂)₃ CH₃, (H₃ C)₂ SiCl--O(CH₂ CH₂O)₅ CH₃, Ph(H₃ C)SiCl--(CH₂)₆ O(CH₂ CH₂ O)₅ CH₃, (H₃ C)₂ Si(OCH₂ CH₂CH₃)--(CH.sub. 2)₃ O(CH₂ CH₂ O)₇ CH₃ and (H₃ C)₂ SiCl--(CH₂)₃ O(CH₂ CH₂CH₂ CH₂ O)₃₃ (CH₂)₃ CH₃, where Ph is a phenyl radical, preference beinggiven to (H₃ C)₂ SiCl--(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃, (H₃ C)₂Si(OCH(CH₃)₂)--(CH₂)₃ O(CH₂ CH₂ O)₁₅ CH₃, and (H₃ C)₂ Si(OCH₃)--(CH₂)₃O(CH₂ CHCH₃ O)₆₆ (CH₂)₃ CH₃.

Examples of silanes of formula (IX) are SiCl₃ --(CH₂)₃ O(CH₂ CH₂ O)₅CH₃, Si(OCH₃)₃ --(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃, Si(OCH(CH₃)₂)₃ --(CH₂)₃ O(CH₂CH₂ O)₅ CH₃, Si(OCH(CH₃)₂)₃ --(CH₂)₃ O(CH₂ CH₂ O)₁₅ CH₃, Si(OCH₂ CH₃)₃--(CH₂)₃ O(CH₂ CH₂ O)₄₄ CH₃, Si(OCH₃)₃ --(CH₂)₃ O(CH₂ CHCH₃ O)₂₄ (CH₂CH₂ O)₄₈ (CH₂)₃ CH₃, Si(OCH₃)₃ --(CH₂)₃ O(CH₂ CHCH₃ O)₆₆ (CH₂)₃ CH₃,SiCl₃ --O(CH₂ CH₂ O)₅ CH₃, Si(OCH₂ CH₂ CH₃)₃ --(CH₂)₃ O(CH₂ CH₂ O)₇ CH₃,SiCl₂ (OCH₂ CH₃)--(CH₂)₃ O(CH₂ CH.sub. 2 O)₃ CH₃, SiCl₃ --(CH₂)₃ O(CH₂CH₂ CH₂ CH₂ O)₃₃ (CH₂)₃ CH₃, Si(OCH₃)₃ --(CH₂)₃ O(CH₂ CH₂ O)₁₅ OCCH₃ andSi(OCH₃)₃ --(CH₂)₃ O(CH₂ CH₂ O)₄₄ OCCH(CH₃)₂, preference being given toSiCl₃ --(CH₂)₃ O(CH₂ CH₂ O)₅ CH₃ and Si(OCH₂ CH₃)₃ --(CH₂)₃ O(CH₂ CH₂O)₄₄ CH₃.

Examples of silanes of formula (X) are SiCl₄, Si(OCH₃)₄, Si(OCH₂ CH₃)₄,Si(OCH(CH₃)₂)₄, Si(OCH₂ CH₂ CH₃)₄, Cl₂ Si(OCH₃)₂, ClSi(OCH₂ CH₃)₃,Si(OOCCH₃)₄ and (H₃ CCOO)Si(OCH₂ CH₃)₃, preferably SiCl₄ and Si(OCH₂CH₃)₄.

Examples of silanes of formula (XI) are H₃ CSiCl₃, H₃ CSi(OCH₃)₃, H₃CSi(OCH(CH₃)₂)₃, H₃ CSi(OOCCH₃)₃, H₃ CSi(OCH₂ CH₃)₃, H₂ C═CH--SiCl₃, H₂C═CH--Si(OCH₂ CH₃)₃, H₂ C═CH--Si(OOCCH₃)₃, F₃ CCH₂ CH₂ --SiCl₃, F₃ CCH₂CH₂ --Si(OCH₂ CH₃)₃, PhSiCl₃, PhSi(OCH₃)₃, HS--(CH₂)₃ --Si(OCH₃)₃ andHS--CH₂ --Si(OCH₃)₃ where Ph is a phenyl radical, preference being givento H₃ CSiCl₃, H₃ CSi(OOCCH₃)₃, H₃ CSi(OCH₂ CH₃)₃ and HS--(CH₂)₃--Si(OCH₃)₃.

Examples of silanes of formula (XII) are H--Si(OCH₃)₃, H--Si(OCH₃)₂ CH₃,H--Si(OCH₃)₂ Cl, H--Si(OCH₃)₂ N(CH₃)₂, H--Si(OCH₂ CH₃)₃, H--Si(OCH₂CH₃)₂)₂ CH₃, H--Si(OCH₂ CH₃)₂ Cl, H--Si(OCH₂ CH₃)₂ N(CH₃)₂,H--Si(OCH(CH₃)₂)₃, H--Si(OCH₃)(OCH(CH₃)₂), H--Si(OCH₂ CH₂ CH₃)₃ andH--Si(OCH₂ CH₂ CH₂ CH₃)₂ (OCH₃), preferably H--Si(OCH₂ CH₃)₃ andH--Si(OCH (CH₃)₂)₃.

Examples of organopolysiloxanes of formula (III) are those of theaverage formula

    ______________________________________                                        [HSi(OEt).sub.2 O.sub.1/2] ].sub.1.4 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.6       [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.4.8 Me]O.sub.2/2          ].sub.20 [SiMe.sub.2 O.sub.2/2 ].sub.53.3                                     [SiO.sub.4/2 ].sub.0.5                                                        [HSi(OEt).sub.2 O.sub.1/2 ].sub.3.1 [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2       CH.sub.2 O).sub.14.8 Me]O.sub.2/2 ].sub.12                                    [SiMe.sub.2 O.sub.2/2 ].sub.43.5 [MeSiO.sub.3/2 ].sub.1.5                     [HSiMe(OMe)O.sub.1/2 ].sub.3.6                                                [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CHCH.sub.3 O).sub.24 (CH.sub.2            CH.sub.2 O).sub.48 Me]O.sub.2/2 ].sub.12                                      [(F.sub.3 CCH.sub.2 CH.sub.2)SiMeO.sub.2/2 ].sub.235 [PhSiO.sub.3/2           ].sub.2.5                                                                     [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.57 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.43      [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.5.3 Me]O.sub.2/2          ].sub.9.6 [SiMe.sub.2 O.sub.2 ].sub.35.4                                      [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.58 [EtOSiMe.sub.2 O.sub.1/2 ]               .sub.0.42                                                                     [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.5.2 Me]O.sub.2/2          ].sub.8 [SiMe.sub.2 O.sub.2/2 ].sub.110                                       [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.78 [Me.sub.3 SiO.sub.1/2 ].sub.0.22         [MeSi[(CH.sub.2).sub.6 --O(CH.sub.2 CH.sub.2 O).sub.5 CH.sub.3 ]O.sub.2/2     ].sub.34 [SiMe.sub.2 O.sub.2/2 ].sub.332                                      [HSi(OEt).sub.2 O.sub.1/2 ].sub.3.9 [Me.sub.2 Si[(CH.sub.2).sub.3             --O(CH.sub.2 CH.sub.2 O).sub.15.8 Me]O.sub.1/2 ].sub.0.2                      [SiMe.sub.2 O.sub.2/2 ].sub.32 [SiMeViO.sub.2/2 ].sub.6 [MeSiO.sub.3/2        ].sub.2.5                                                                     [HSi(OiPr).sub.2 O.sub.1/2 ].sub.2.9 [Si[(CH.sub.2).sub.3 --O(CH.sub.2        CH.sub.2 O).sub.5.3 Me]O.sub.3/2 ].sub.1.2                                    [SiMe.sub.2 O.sub.2/2 ].sub.24                                                [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.7 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.3        [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.4.8 Me]O.sub.2/2          ].sub.12 [SiMe.sub.2 O.sub.2/2 ].sub. 130.3                                   [SiMeViO.sub.1/2 ].sub.6 [SiMe[(CH.sub.2).sub.3 --SH]O.sub.2/2 ].sub.3.7      [HSi(OiPr).sub.2 O.sub.1/2 ].sub.1.8 [iPrOSiMe.sub.2 O.sub.1/2 ].sub.0.2      [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CHCH.sub.3 O).sub.66 (CH.sub.2).sub.3     CH.sub.3 ]O.sub.2/2 ].sub.12 [SiMe.sub.2 O.sub.2/2 ].sub.221                  [SiMeViO.sub.2/2 ].sub.66 [SiMe[(CH.sub.2).sub.3 --SH]O.sub.2/2 ].sub.32.7    [HSi(OiPr).sub.2 O.sub.1/2 ].sub.2.8 [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2      CH.sub.2 O).sub.15 CH.sub.3 ]O.sub.2/2 ].sub.4                                [SiMe.sub.2 O.sub.2/2 ].sub.17 [Ph(H.sub.3 C)SiO.sub.2/2 ].sub.4              [H.sub.2 C═CH--(CH.sub.2).sub.4 --SiMeO.sub.2/2 ].sub.6 [HS--CH.sub.2     --SiO.sub.3/2 ].sub.2.9                                                       [HSi(OEt).sub.2 O.sub.1/2 ].sub.3.8                                           [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.44 OCCH(CH.sub.3).sub.    2 ]O.sub.2/2 ].sub.8                                                          [SiMe.sub.2 O.sub.2/2 ].sub.113 [2-(3-cyclohexenyl)-ethyl-SiMeO.sub.2/2       ].sub.4.2                                                                     [Si[(CH.sub.2).sub.3 --SH]O.sub.3/2 ].sub.0.7 [SiO.sub.4/2 ].sub.1.1 and      [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.2 [Me.sub.2 SiViO.sub.1/2 ].sub.0.8         [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.3 OCH.sub.3 ]O.sub.2/2     ].sub.8                                                                      [SiMe.sub.2 O.sub.2/2 ].sub.26 [Si[(CH.sub.2).sub.3 --SH]O.sub.3/2            ].sub.0.7                                                                     ______________________________________                                    

where Me is a methyl radical, Et is an ethyl radical, Ph is a phenylradical, and Vi is a vinyl radical, preferably

    ______________________________________                                        [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.4 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.6        [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.4.8 Me]O.sub.2/2          ].sub.20 [SiMe.sub.2 O.sub.2/2 ].sub.53.3                                     [SiO.sub.4/2 ].sub.0.5                                                        [HSi(OEt).sub.2 O.sub.1/2 ].sub.3.1 [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2       CH.sub.2 O).sub.14.8 Me]O.sub.2/2 ].sub.12                                    [SiMeO.sub.2/2 ].sub.43.5 [MeSiO.sub.3/2 ].sub.1.5                            [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.57 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.43      [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.5.3 Me]O.sub.2/2          ].sub.9.6 [SiMe.sub.2 O.sub.2/2 ].sub.35.4 and                                [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.7 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.3        [MeSi[(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.4.8 Me]O.sub.2/2          ].sub.12 [SiMe.sub.2 O.sub.2/2 ].sub.130.3                                    [SiMeViO.sub.2/2 ].sub.6 [SiMe[(CH.sub.2).sub.3 --SH]O.sub.2/2 ].sub.3.7      ______________________________________                                    

The process has the advantage that the organopolysiloxanes containinghydrophilic groups can be prepared in a very simple manner fromavailable industrial materials. It is possible to prepare a multiplicityof different products having a very specific property profile.

Another advantage of the process is that there is no need for anyorganic solvent.

The organopolysiloxanes containing hydrophilic groups can be crosslinkedin a known manner by intake of moisture, making it possible for themoisture crosslinking to be accelerated by addition of carboxylic acids,such as oleic acid or 2-ethylhexanoic acid. If the organopolysiloxanes,in addition to hydrophilic groups, also contain photocrosslinkablegroups such as vinyl groups or mercapto groups, they can be crosslinkedby means of high-energy radiation, it being possible for the radiationcrosslinking to be accelerated by addition of suitable photoinitiators.For both moisture crosslinking and radiation crosslinking, see the abovementioned WO 93/00405.

The organopolysiloxanes containing hydrophilic groups can be usedwherever permanent hydrophilicity is desired, particularly where thehydrophobicity of moisture-crosslinkable silicones have previouslyprevented them from being used and the advantages of rapid moisturecrosslinking catalyzed under mild conditions have a beneficial effect,for example

as component of coating materials for textiles, wood, glass, concrete,stone, paper, cardboards, cork, ceramics, plastic sheets, such as PVCsheets, polyester sheets, PE sheets, metal objects and bonded fabrics;

as component of primers for improving water wettability or adhesion ofRTV 2-component addition silicone rubber, RTV 2-component condensationsilicone rubber of RTV 1-component condensation silicone rubber, forexample in order to enable vulcanized products to be overcoated withwater-containing paint emulsion, or as soil-release additive;

as component of RTV 2-component addition silicone rubber, RTV2-component condensation silicone rubber or RTV 1-component condensationsilicone rubber compositions for improving water wettability, forexample in impression compounds (hydrophilic modifier which can beincorporated by crosslinking);

as component of electrically conductive mixtures, for example in drybatteries;

as component of implants for improving tissue compatibility or indrug-release implants or other active compound-releasing mixtures(fungicides, bactericides etc.) for improving the controlled release ofactive compound;

as component of antifogging and deicing coatings, for example forvehicle and airplane windows, or of antifouling coatings for ship hulls,and

as a degassing additive or compatibilizer in coatings and paints.

If the organopolysiloxanes contain not only moisture crosslinkable butalso radiation crosslinkable groups, they can also be used in the areasof application given in the above mentioned WO 93/00405.

In the examples described below, parts and percentages are by weight,unless otherwise stated. Unless stated the examples below are carriedout at a pressure of the surrounding atmosphere, i.e., at about 1000hPa, and at room temperature, i.e., at about 23° C., or at a temperatureobtained upon combining the reactants at room temperature withoutadditional heating or cooling. The relative humidity is between 60% and80%, unless stated otherwise. All viscosities given below are based on atemperature of 25° C.

Abbreviations below are,

Me is a methyl radical

Et is an ethyl radical

Vi is a vinyl radical

iPr is an iso-propyl radical.

EXAMPLE 1

(a) Silane synthesis:

A mixture of 1000 g of a polyglycol ether of the average formula H₂C═CHCH₂ (OC₂ H₄)₄ OMe (sold by Hoechst AG under the name "Polyglycol AM250") and 14.6 g of 1% solution of thebis(1,1,3,3-tetramethyl-1,3-divinyldisiloxane)-Platinum complex inhexane (=100 ppm of Pt) is made to react with 460 g ofdichloromethylsilane at 70° C. After distilling of the volatiles at 50°C./4 hPa, 1326 g of a yellowish oil remain as residue which is reactedwith 1440 g of isopropanol Distillation up to 200° C./2 hPa gives 822 gof a yellowish liquid of the average formula MeSi(OiPr)₂ --(CH₂ CH₂O)₄.8 Me as residue.

(b) Polysiloxane Synthesis:

0.14 g of phosphonitrile chloride ("PNCl₂ ") is added at roomtemperature to 100 g of an OH--terminated polydimethylsiloxane having achain length of about 220 Me₂ SiO units (viscosity=1 Pa.s; sold byWacker-Chemie GmbH) and 2.5 g of SiCl₄, and the resulting mixture isheated to 100° C. with stirring. 93 g of MeSi(OiPr)₂ --(CH₂ CH₂ O)₄.8Me, the preparation of which is described above under (a), are meteredin at 100° C. over a period of one hour. After addition of a further0.14 g of PNCl₂, stirring at 100° C. is continued for another hour. Themixture is then hydrolyzed with 45 ml of water. Volatiles are distilledoff at 130° C./2 hPa. After cooling to 110° C., 1 g of BHT(=2,6-di-t-butyl-p-methylphenol) and 30 g of triethoxysilane are addedto the reaction mixture, which is then refluxed for one hour untilexcess silane is distilled off at 120° C./3 hPa. This leaves a residueof 125 g of a clear oil having a viscosity of 90 mm² /s, which, based onthe ²⁹ Si and ¹ H NMR spectra can be assigned the following averageformula:

    [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.4 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.6 [MeSi{(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.4.8 Me}O.sub.2/2 ].sub.20 [SiMe.sub.2 O.sub.2/2 ].sub.53.3 [SiO.sub.4/2 ].sub.0.5.

EXAMPLE 2

23.6 g of dichloromethylvinylsilane and 0.09 g of PNCl₂ are added at 90°C. to a mixture of 315 g of an OH-terminated polydimethylsiloxane havinga chain length of about 420 Me₂ SiO units (viscosity 6 Pa.s; sold byWacker-Chemie GmbH), 60.4 g of an OH-terminated polysiloxane of theaverage formula HO(SiMe₂ O_(2/2))₉.6 (SiMeVi_(2/2))₂.4 H (sold byWacker-Chemie GmbH) and 0.21 g of BHT (=2,6-di-t-butyl-p-methylphenol).28.9 g of the silane of the formula Me(MeO)₂ Si(CH₂)₃ --SH are meteredin over a period of 45 minutes. After repeated addition of 0.09 g ofPNCl₂, 200 g of MeSi(OiPr)₂ --(CH₂)₃ --O(CH₂ CH₂ O)₄.8 Me, thepreparation of which is described in Example 1 under (a), are metered inat 90° C. over a period of one hour. The mixture is stirred at 100° C.for one hour. It is then hydrolyzed with a solution of 15 g of sodiumbicarbonate in 200 ml of water. Volatiles are distilled off at 130° C./1hPa. After cooling to room temperature, 2 g of BHT(=2,6-di-t-butyl-p-methylphenol) and 103 g of triethoxysilane are addedto the reaction mixture, which is then refluxed for one hour beforeexcess silane is distilled off at 120° C./1 hPa. Filtration of theresidue gives 427 g of a clear yellowish oil having a viscosity of 330mm² /s, which, based on the ²⁹ Si and ¹ H NMR spectra can be assignedthe following average formula:

    [HSi(OEt).sub.2 O.sub.1/2 ].sub.1.7 [EtOSiMe.sub.2 O.sub.1/2 ].sub.0.3 [MeSi{(CH.sub.2).sub.3 --O(CH.sub.2 CH.sub.2 O).sub.4.8 Me}O.sub.2/2 ].sub.12 [SiMe.sub.2 O.sub.2/2 ].sub.130.3 [SiMeViO.sub.2/2 ].sub.6 [SiMe(CH.sub.2).sub.3 --SH O.sub.2/2 ].sub.3.7.

EXAMPLE 3

10 g of the siloxane from Example 1 are knife-coated onto a glass platein a film thickness of about 0.1 mm. A sample of the substrate thuscoated exhibits a skinning time of 15 minutes in the presence of air.

EXAMPLE 4

10 g of the siloxane from Example 2 are thoroughly mixed with 0.1 g ofoleic acid and 0.4 g of 2-hydroxy-2-methyl-1-phenyl-1-propanone (sold byMerck, Darmstadt, FRG, under the name Darocure 1173). The mixture thusobtained is knife-coated onto a glass plate in a film thickness of about0.1 mm. A sample exhibits a skinning time of 20 minutes in air in theabsence of light.

Another sample of the substrate thus coated is irradiated in thepresence of air by irradiating the coating with UV light for 10 secondsat an output of 80 watt/cm of illuminated length and output maxima at awavelength of 313 nm and 361 nm at a distance of 15 cm from the surfaceto be crosslinked (UV laboratory dryer, model 22/3, from Bentron GmbH,Rodermark, FRG), as a result of which the coating is cured to give a drysurface. One drop of demineralized water is applied to the coated glassplate thus obtained by means of a pipette. After 30 seconds, thediameter of the wetted area has doubled.

Comparative Example 1

(water wettability)

2400 g of α,ω-dihydroxydiorganopolysiloxane containing, as thediorganosiloxy units, on average 60 dimethylsiloxy units, 4vinylmethylsiloxy units and 2 HS(CH₂)₃ SiCH₃ O_(2/2) units and having aviscosity of about 100 mPa.s, 328 g of hydrogentriethoxysilane and 13.6g of pentanedione are thoroughly mixed in the absence of moisture, themixture is heated to 100° C., stirred at 100° C. for 1 hour, and thevolatiles are removed by brief evacuation (15 minutes/1 mbar). Themixture is then filtered through cellulose. This gives 2513 g of a clearcolorless oil having a viscosity of 118 mPa.s which, based on ²⁹ Si NMRspectroscopy, contains 93% of H--Si--(OEt)₂ terminal groups, relative tothe number of all terminal groups.

100 parts of this siloxane are thoroughly mixed with 1 part of oleicacid and 0.2 part of 2-hydroxy-2-methy-1-phenyl-1-propanone (sold byMerck, Darmstadt, FRG, under the name Darocure 1173). The mixture thusobtained, which is a clear colorless oil having a viscosity of 116mPa.s, is knife-coated onto a glass plate in a film thickness of about0.1 mm. A sample of the substrate thus coated is irradiated in thepresence of air by irradiating the coating with UV light for 10 secondsat an output of 80 watt/cm of illuminated length and output maxima at awavelength of 313 nm and 361 nm at a distance of 15 cm from the surfaceto be crosslinked (UV laboratory dryer, model 22/3, from Bentron GmbH,Rodermark, FRG), as a result of which the coating is cured to give a drysurface.

One drop of dimineralized water is applied to the coated glass platethus obtained by means of a pipette. After 30 minutes, shape and wettingarea of the water drop are unchanged.

What is claimed is:
 1. An organopolysiloxane comprising at least oneunit (A) of the formula

    (R.sup.3 O).sub.m SiHR.sub.2-m O.sub.1/2                   (I)

and at least one unit (B) selected from the group consisting of ER₂SiO_(1/2), ERSiO_(2/2) and ESiO_(3/2), in which R is a monovalentSiC-bonded optionally substituted hydrocarbon radical having 1 to 12carbon atoms, R³ is a monovalent optionally substituted hydrocarbonradical, m is 1 or 2, and E is a radical of the formula

    --R.sup.1.sub.n [OY].sub.x R.sup.2                         (II)

in which R¹ is an alkylene radical having 1 to 6 carbon atoms, n is 0 or1, Y is alkylene groups having 1 to 4 carbon atoms, R² is an alkoxyradical having 1 to 6 carbon atoms or an oxycarbonylalkyl radical having1 to 6 carbon atoms, and x is an integer from 1 to
 200. 2. Anorganopolysiloxane as claimed in claim 1, wherein the proportion ofsiloxane units (A) is between 0.2% and 67%, relative to the total numberof the siloxane units present in the organopolysiloxane.
 3. Anorganopolysiloxane as claimed in claim 1, wherein the proportion ofsiloxane units (B) is between 1% and 70%, relative to the total numberof the siloxane units present in the organopolysiloxane.
 4. Anorganopolysiloxane as claimed in claim 1, wherein the organopolysiloxaneis one of the formula

    [(R.sup.3 O).sub.m HSiR.sub.2-m O.sub.1/2 ].sub.a [(R.sup.3 O)R.sub.2 SiO.sub.1/2 ].sub.b [ER.sub.2 SiO.sub.1/2 ].sub.c [ERSiO.sub.2/2 ].sub.d [R.sub.2 SiO.sub.2/2 ].sub.e [SiO.sub.4/2 ].sub.f [RSiO.sub.3/2 ].sub.g [ESiO.sub.3/2 ].sub.h                                     (III)

in which R, E, R³ and m have the above mentioned meaning and a is from 1to 8, b and c are each from 0 to 8, d is 0 to 280, e is 0 to 396, f is 0to 3, g is 0 to 6, and h is 0 to 3, wherein a+b+c is 2 to 8, c+d+h is 1to 280, a+b+c+d+e+f+g+h is 3 to 400, and the ratio of the sum ofa+b+e+f+g to that of c+d+h is 100:1 to 1:1.
 5. An organopolysiloxane asclaimed in claim 1, wherein the organopolysiloxane contains SiC-bondedmercapto-substituted hydrocarbon radicals and SiC-bonded radicals havingan aliphatic carbon-carbon multiple bond.
 6. An organopolysiloxane asclaimed in claim 5, wherein the ratio of SiC-bonded mercapto-substitutedhydrocarbon radicals to the SiC-bonded radicals having an aliphaticcarbon-carbon multiple bond is between 10:1 and 1:10.
 7. A process forpreparing organopolysiloxanes as claimed in claim 1, comprising in afirst step reacting;A a silane of the formula

    ERSiZ.sub.2                                                (IV),

with B compounds selected from the group consisting of the generalformulae

    R.sub.2 SiZ.sub.2                                          (V),

    HO(SiR.sub.2 O).sub.i H                                    (VI),

and

    (SiR.sub.2 O).sub.j                                        (VII),

and in a second step reacting the product of the first step with asilane of the general formula

    (R.sup.3 O).sub.m HSiR.sub.2-m X                           (XII),

in whichE is a radical of the formula

    --R.sup.1.sub.n [OY].sub.x R.sup.2                         (II)

whereR¹ is an alkylene radical having from 1 to 6 carbon atoms n is 0 or1 Y is an alkylene group having from 1 to 4 carbon atoms R² is an alkoxyradical having 1 to 6 carbon atoms or an oxycarbonylalkyl radical havingfrom 1 to 6 carbon atoms, and x is an integer from 1 to 200; R is amonovalent SiC-bonded optionally substituted hydrocarbon radical havingfrom 1 to 12 carbon atoms, R³ is a monovalent optionally substitutedhydrocarbon radical X is a halogen atom, --OR³, --NR--C(═O)R, --OC(═O)Ror --NR₂, Z is a hydroxyl group, a halogen atom, an alkoxy radical or anoxycarbonylalkyl radical, i is an integer from 2 to 2000, j is aninteger from 3 to 6, and m is 1 or 2.